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Proceedings of the Chemical Society, Vol. 7, No. 92 |
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Proceedings of the Chemical Society, London,
Volume 7,
Issue 92,
1891,
Page 15-22
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. No.92. Session 1890-91. Februa1.y 5th, 1891. Dr. W. J. Russell, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Illessrs. Albc1.t Edward Bell, Sherborne School, Slierborne, Dorset ; Rhys Pendrill Charies, Plm Newydd, Neath ; Gilbert John Fowler, Dalton Hall, Victoria Park, Manchester ; Berington H. Gibbins, Ocala, Ploridw, U.S.A., J. A. R. Greaves, Old Rectory, Grappenball, Chesliirc>; William Beaumont Hart, Gransmoor Avenue, Fairfield, near Man-Chester; Rev. Edgar Norman Langham, M.A., St. John’s Collegr, Cambridge ; James Leicester, 3, Queen’s Parade, Brandoii Hill, Bristol ; William Macdonald, 109, CroFton Road, Peckham, S.E. ; Frederick Johnson Merrils, 65, Roe Lane, Pitsmoor, Sheffielcl; George R.Morrison, Richmond House, Plaistow ; Lewis Ougli, 15, Upper King Street, Leicester ; James Ashburner Storey, 21001-side, Lancaster ; Albert Searl, The Caxtons, Miskin Road, Dartforcl. It,was announced that the following changes in the Couiicil list were proposed by the Council:- As President, Professor Crum Brown, vice Dr. Russell. As Vice-presidents, Mi-. J. Pattinson and Professor Tilden, rice Professors Crum Brown and Mallet. As Foreign IYecretary, Professor Meldola, zice Professor Jap p. As Neinbers of Cou1zciZ, Dr. Atkinson, Mr. Bovertou Redwood, Pro-fessor Perkin and Dr. J. Voelcker, vice Nr. Cross, Professor Dunstan, Professor hleldola and Dr. Plimpton. The following papers were read :-5.“ The formation of an explosive substance from etller.” By Professor Y.T. Cleve. The author, in the course of a letter to the Secretary, describes a 16 remarkable explosion occasioned by impurities in ccjmmercial ethei.. On distilling about 250 C.C. of the ether, it was noticed that a viscid residue remained; after drying on the water bsth, this formed A t'ransparent, amorphous mass, estimated to weigh about 0.75 gram. Professor Clele states that, having poured a little water on to tlitb substance, he proceeded to stir. it gently with a rounded glass rod ; this occasioned a most violent explosion. A number of the pieces of glass which were projected about peyforated the windows just ns it' they had been revolver bullets. The explosive substance was probablj-ethyl peroxide, as it gave the well-known perchromic colorntioii. besides liberating iodine and discharging oxygen from silver oxide ; it was at once destroyed by reducing agents; it exploded with ;is much violence as if it had been chloride of nitrogen or fulminate.D1scushlox. Professor DUNSTANremarked that several cases Had been recorded of explosions during the distillation of impure ether, oue a few years ago by Schaer in tlie Aduiv dey Pliarmt-ccie for 1877. 6. "Does magnesium form compounds with hydrocarbon radicles ?" By Ornie BIasson, M.A., D.Sc., and U. T. BI. Wilsmore, B.Sc., University of Me1 bourne. According to Hallwachs and Schafarik (Annnlen, 109,ZOS), mag-nesium in the form of filings and ethyl iodide commence to infewict at ordinary temperatures, and the interaction is complete at 180"; they state that the metal becomes converted into a white mam, the liquid disappearing, much gas being generated.On heating .the white mass, a colourless, volatile liquid distilled over, which fumed strougly in the air but did not iuiiame ; this iiquid, it was believetl, consisted of hydrocarbons mixed with traces of niagnesiuin ethidc, but, as the residue decomposed water with explosive violence, it was thought that it cootained a coilsiciei*able amount oE niagnesiuiii ethide combined with iiiaguesium iodide. Cahours (Annules de Chimis et de Physique [5],18,17) also found that much heat was evolved on adding methyl or ethyl iodide to mag-nesium filings.Haviiig digested a mixture of the metal and ethyl iodide at 130"till the liquid had disappeared, he heated the resulting while mas3 in an ntniospliere of hydrogen, and obtained a liquid dis- tillate which took fire in the air and acted strongly on wateia. Carbon and hydrogen were estimated in two fractions of this liqni(l, but the results were Gar from agreeing with the theoretical values ; tlie discrepancies were attributed to insufficient purification. No evidence of the piwenee of magiiesiuni in the product was adducetl by Cahours. Wanklyn heated sodicm 7inc ethide with mercury and magnesium wi~e,and obtained a white, spontaneously inflammable, solid prodiict. r1lhis contained magnesium and zinc, but only traces of sodium; it was believed to be magnesium zinc ethide.The authors state that they have in vain endeavoured to prepare magnesium ethide (1) from magnesium and ethyl iodide; (2) from magnesium-copper couples and ethyl iodide ; (3) froin an alloy of magnesium and sodium and ethyl iodide ; (4)from magnesium and zinc ethide ; (5) from magnesium and mercury ethide ; and (6) from anhydrous magnesium iodide and zinc ethide. An alloy formed by heating magnesium and Rodium together in a hard glass flask in an atmosphere of hydrogen acted very slowly on ethgl iodide at loo", and no signs of the formation of magnesium et'liide were observed. On heating together magnesium and zinc 01' mercury etliide in sealed tubes, 110 action occurred till the tempera- tnre rose sufficiently high to decompose the ethide ; large quantities of gas were then formed, zinc or mercury separating, but no magne-sium ethide.Similarly, magnesium iodide and zinc ethide appeared not to interact, the ethide being decomposed simply by t,he heat. There appeared to be little or no advantage in using niagnesium- copper couples, the action being in all respects similar to that oE mag-nesium alone, although occasionally somewhat quicker. Magnesium iodide and gnseons 1i.ydrocnrbons were the sole products. Several experiments on the action of ethyl iodide on inagnesium were tried under varied conditions and using the two substances in different proportions ; sometimes a crystal of iodine was a<dded as iwommended by Frankland for the preparation o€ zinc chloride. In most cases the materials were heated together in a flask connected to a reflux condenser, from which the air was displaced at the outset by hydrogen or carbon dioxide.The magnesiam used was prepared by fusing conimercial rihbon in an iron crucible under a flux of am-monium, magnesium and potassium chlorides, and subsequently filing down the lump ; it was practically free from impurities except tmces of iron. Tlie results obtained were nniformly negative, and iIltho~1~hprevious observers have stated that interaction occurs at ordinary temperatures, the authors have never perceived the slightest sign of action till after the iodide and metal had been heated together foi. sonie time. Thus in an experiment in which 30 grams of specia11:-dried ethyl iodide was added to 5 grams of magnesium, ailcl tlie tempt~ature of the bath containing the flask was maintained a little below loo", no action seemed to take place f01.a time, but after :I while gas was given off and a white powder was seen to slowl,~form 011 the mctal; after 30 hours' continuous Iicatiug, ethyl ioiiitle ceased to run back, and the evollltion of gas - which had been continuous-came to an end. On heating the residue to 270", no distillate except a little unused iodide W;LR obtained ; the residue proved on analysis to be simply magnesium iodide. In no case was a trace of distillate obtained showing ally tendency to fume in the air. The authors point out that magnesium iodide is very hygroscopic, and is so violently acted on by water that they are inclined to think that Hallwachs and Schafarik may possibly have been led to suppose that magnesium ethide in combinatioil was present when really there was only mitgnesium iodide.Magne-sium iodide forms a crystalline compound with ether w hicli apparently has the composition MgI2*2Et,O. The authors are hence inclined to concludz that previous experi- menters have used magnesium containing some impurity which fitcilitated its action on the iodide ; but they do not Eee reason for assuming that the yesult was the production of magnesium ethide. 1)1hey also suggest that possibly the magnesium previously used may have contained zinc, and that small quantities of zinc ethide niixed with hydrocarbons may have been mistaken for magnesium ethide.The results, however, raise a question of no slight interest,. Of the elements of the second natural group, zinc and mercury very iteadily form compounds with hydrocarbon radicles ; cadiniuin appears to be capable of forming them though much less readily; and beryllium propide and ethide have been described by Cahours. G'dcinm, strontium and barium, on the other hand, presumably do iiot form such compounds. In which sub-group must magnesium be placed according to this test P Agaiii, alumininm, which follows nragiiesium in sei ies, forms well defined compounds with hydrocarbon radicles, while sodiurri, which precedes it, forms only an utlstab'e clouble compound with zinc and ethyl.Which does niaqnesiuui resemble, if eitlrer P Or has it an intermediate character? It is exceptional for elements on the descending poi-tions of the curve of atomic volumes to unite with hydrocarbon radicles, and a glarice at the curve shows that beryllium and magnesium are the only elements uiidoubtedly occupying such a position that are believed to do so. As to beryllium, it may be pointed out that Cahours (Coiiyf. rewd., 76, 1383) worked with very small quantities and apparently basctl his conclusions on purely qualitative ob~ervat~ions. With regard to magnesium, the authors think that the extremely slight character of the older evidence and the fact that their own experiments have lccl to directly contrary conclusions to those of Cahours justify them iii denying its power to form free compounds of the kind discussed.It is, however, just possible that, as indicated by Wanklyn's qualitative experiment, magnesium may form an unstable donble etliide with zinc, thus resembling sodium, which immediatelg precedes it in the natural classification. DI scusSIOX. Dr. ARMSTRONGsaid that Messrs. Masson and Wilsmore’s paper had been despatched from Melbourne on December 29t’h ; meanwhile the question which they had put, and to which they inclined to give R negative reply, had been answered in the affirmative by Lohr iu one of the latest numbers of Liebiy’s AnnaZen (261,72). Lol~r,like the authors, had found that methyl and ethyl iodides had no action at ordinary temperatures either on magnesium alone or on magnesium as,c.ociated with copper or sodium; and that the action was very sluggish at high temperatiires. The presence of a little ethylic: acetate served, however, to cause an inter.action to set in vigorously in the cold, which was completed within 40 to 50 hours at 110”; but the product gave no liquid distillate even at 330”,and Lohr had estab- lished the interesting fact that magnesium methide and ethide were solid, non-volatile componnds.These observations, taken in conjunction with tliose of the eay:ier workers in the sctme field, afforded further evidence that in the forma-tion of organo-metallic compounds, as in so many other cases, it was necessary that some third substance should he present to conditiou i11te rac tion.Referring to the authors’ suggestion, that the niagnesiiim used by previous workers contained zinc, Professor THORPEsaid that he had Lad occasion when at the Owens College to analjse a large number of s:tmples of mqpesium from Mr. Sonstadt, who in those days was the sole maker of the metal, and these never contained zinc, so that he cwuld not agree with the authors in their explanation. 7. “Compounds of the oxides of phosphorus with sulphuric ail-liydride.” By R.H. Adie, B.A. The aiithor has endeavoured to prepare compounds of phosphorus similar to those which the other elements of the group form wit11 solphuric anhjdride. Employing a preparation obtained from Messrs. Harrington, of Cork, approximately consisting of H3PO3,he obtained, by the actioii of sulpliuric anhydride, a product very nearly of the composition corresponding to the formula H,P04-3S0,= (SO,H),PO,, in the form of a viscid liquid which was decomposed by water, but without violence, yielding sulphuric and orthophosphoric, and but traces of metac- and pyro-phosphoric acids.Sulphuric anhydride and phos-~IJO~USfound to interact violently ; the author represents the were 20 product by tlie formula 3P20,-2S0,. Tlie compound slowly decorn- posees into phosphoric and sulphui*ons anliydrides ; it is instantly decomposed by water, but the phosphorus containing part dissolves only very slowl~-. DrscL.ssloN. Profcssor RAMSAY,after referring to the interest attaching to the investigation of compounds such as were described by the author, expressed the opinion that they were legitinifltely regarded as salts.and thatl the existence of such salts must serve to break down thc distinction which was usually made between nietals and non-metals based on the formation OE salts. dissented from this view. He also took occasion Professor THORPF: to correct the statement made by Mr. Tutton and himself, that thp oxide P40, becomes red on exposui*e to light ; this change, they had since discovered, was due to the presence of a small quantity of' plios phoru s. 8. " Combustion of magnesium in water-vapour." By G. T. Moody, D.Sc. The author points out that the combustion of magnesium in water- vapour, which is very difficult to conduct in the manner commonly de- scribed (cf.Kessler, Uer., 2, 36!4), may be conveniently demonstrated, as a lecture experiment, by carrying out the operation in a piece of hard glass tube, of about 10 mm. in diameter and 250 mm. in length, bent at an angle of 120" so as to leave one arm nearly twice as long as the othei.. The shorter arm is inserted throngh a cork closing the mouth of ;I "tin-can " or other convenient vessel, in which steain can be gene- rated ; and the longer arm, which coiitains a few strips of m~gnesiuni ribbon, is connected by a fairly wide delivery tube with the pneumatic. trough, at whicli the liberated h.ydrogen may be collected. When tbe air in the apparatus has been displaced by a slow current of steam, the arm in tlie tube containing the magnesium is cautiously heated by means of a bunsen burner until the temperature of the tube is considerably higher than that at which water-vapour condenses ; the bmsen burner is then replaced by a blowpipe flame, which is moved about in such a way that the whole of the arm becomes very hot, and 011 allowing the flame to impinge for a few seconds on a portion of the tiibe against which the magnesium rests, the metal takcs fire and biirny with great brilliancy.The success of this experiment is only assured when there is a very slow current of steam passing through the apparatus, and when the tube containiiig the magnesium is carefully heated, as in the mBnner 21 above described.Uiider siich circumstaiices, the metal burns with great regularity, fracture of the tube being usually avoided, snd the whole of the hydrogen evolved may be collected. At the next meeting, on February 19th, there will hs a ballot for the candidates whose names and qualifications were set forth in the last number of these Proceedings. The following papers will be read :-“ The synthesis of dimethyldihydroxyhept,zmethylene.” By Dr. Kipping and Professor Perkin. “ The osmotic pyessui-cs of s,dts in solution.” By R. H. Adie,-B.A. 22 CHEMICAL SOCIETY’S JUBILEE. Fellom are requested to note-That the afternoon meeting on Febrnary 24t31 will be held irt the ‘I’heatre of the London Universit.y, Burlingtori Gardens, W., at 3 till 5 o‘clock P.M.; the number who have announced their intention of attending being larger than can be accommodated at the Society of Arts.The presence of ladies is desired. The President and Council will hold a reception in the evening at 8.30 o‘clock, in the Hall of the Goldsmiths’ Company, Foster Lane, E.C., the use of which, for the purpose, has been kiiidly granted to them by the Worshipful Company of Goldsmiths. On February 25th, the Fellows and their friends will dine at the I!hitehall Rooms, Hate1 M6tropole, at 6.30 for 7 o’clock. Price of dinner tickets, One Guinea, to be paid in advanse. Fellows desiriiig to be present, who have not yet made applicat’ion for dinner tickets, are urgently requested at oiice to give the necessary notice. HAILHISON AXD SONS, PI1TXTE:ELSIN OBDINAHl-TO I1EH MAJESTY, bT.MARTIS’S IASI?:.
ISSN:0369-8718
DOI:10.1039/PL8910700015
出版商:RSC
年代:1891
数据来源: RSC
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